Organic element for electroluminescent devices

ABSTRACT

Disclosed is an electroluminescent device comprising a light-emitting layer containing a light emitting material that contains an organometallic complex comprising a metal selected from the group consisting of Pt, Pd and Ir, and a tridentate (N{circumflex over ( )}C{circumflex over ( )}N) ligand, wherein the tridentate (N{circumflex over ( )}C{circumflex over ( )}N) ligand represents a ligand that coordinates to the metal through a nitrogen donor bond, a carbon-metal bond, and a nitrogen donor bond, in that order, wherein at least one of the nitrogen donors is part of an aromatic ring or an imine group. The invention also includes a display or room lighting device employing the device of the invention and a process of emitting light from the device of the invention. The device of the invention provides good luminance efficiency.

FIELD OF THE INVENTION

This invention relates to an organic light emitting diode (OLED)electroluminescent (EL) device comprising a light-emitting layercontaining an organometallic complex that provides desirableelectroluminescent properties.

BACKGROUND OF THE INVENTION

While organic electroluminescent (EL) devices have been known for overtwo decades, their performance limitations have represented a barrier tomany desirable applications. In simplest form, an organic EL device iscomprised of an anode for hole injection, a cathode for electroninjection, and an organic medium sandwiched between these electrodes tosupport charge recombination that yields emission of light. Thesedevices are also commonly referred to as organic light-emitting diodes,or OLEDs. Representative of earlier organic EL devices are Gurnee et al.U.S. Pat. No. 3,172,862, issued Mar. 9, 1965; Gurnee U.S. Pat. No.3,173,050, issued Mar. 9, 1965; Dresner, “Double InjectionElectroluminescence in Anthracene”, RCA Review, Vol. 30, pp. 322-334,1969; and Dresner U.S. Pat. No. 3,710,167, issued Jan. 9, 1973. Theorganic layers in these devices, usually composed of a polycyclicaromatic hydrocarbon, were very thick (much greater than 1 μm).Consequently, operating voltages were very high, often >100V.

More recent organic EL devices include an organic EL element consistingof extremely thin layers (e.g. <1.0 μm ) between the anode and thecathode. Herein, the term “organic EL element” encompasses the layersbetween the anode and cathode electrodes. Reducing the thickness loweredthe resistance of the organic layer and has enabled devices that operatemuch lower voltage. In a basic two-layer EL device structure, describedfirst in U.S. Pat. No. 4,356,429, one organic layer of the EL elementadjacent to the anode is specifically chosen to transport holes,therefore, it is referred to as the hole-transporting layer, and theother organic layer is specifically chosen to transport electrons,referred to as the electron-transporting layer. Recombination of theinjected holes and electrons within the organic EL element results inefficient electroluminescence.

There have also been proposed three-layer organic EL devices thatcontain an organic light-emitting layer (LEL) between thehole-transporting layer and electron-transporting layer, such as thatdisclosed by Tang et al [J. Applied Physics, Vol. 65, Pages 3610-3616,1989]. The light-emitting layer commonly consists of a host materialdoped with a guest material Still further, there has been proposed inU.S. Pat. No. 4,769,292 a four-layer EL element comprising ahole-injecting layer (HIL), a hole-transporting layer (HTL), alight-emitting layer (LEL) and an electron transport/injection layer(ETL). These structures have resulted in improved device efficiency.

Many emitting materials that have been described as useful in an OLEDdevice emit light from their excited singlet state by fluorescence. Theexcited singlet state is created when excitons formed in an OLED devicetransfer their energy to the excited state of the dopant. However, it isgenerally believed that only 25% of the excitons created in an EL deviceare singlet excitons. The remaining excitons are triplet, which cannotreadily transfer their energy to the singlet excited state of a dopant.This results in a large loss in efficiency since 75% of the excitons arenot used in the light emission process.

Triplet excitons can transfer their energy to a dopant if it has atriplet excited state that is low enough in energy. If the triplet stateof the dopant is emissive it can produce light by phosphorescence,wherein phosphorescence is a luminescence involving a change of spinstate between the excited state and the ground state. In many casessinglet excitons can also transfer their energy to lowest singletexcited state of the same dopant. The singlet excited state can oftenrelax, by an intersystem crossing process, to the emissive tripletexcited state. Thus, it is possible, by the proper choice of host anddopant, to collect energy from both the singlet and triplet excitonscreated in an OLED device and to produce a very efficient phosphorescentemission.

One class of useful phosphorescent materials are transition metalcomplexes having a triplet excited state. For example,fac-tris(2-phenylpyridinato-N,C^(2′))iridium(III) (Ir(ppy)₃) stronglyemits green light from a triplet excited state owing to the largespin-orbit coupling of the heavy atom and to the lowest excited statewhich is a charge transfer state having a Laporte allowed (orbitalsymmetry) transition to the ground state (K. A. King, P. J. Spellane,and R. J. Watts, J Am. Chem. Soc., 107, 1431 (1985), M. G. Colombo, T.C. Brunold, T. Reidener, H. U. Gudel, M. Fortsch, and H.-B. Burgi,Inorg. Chem., 33, 545 (1994) Small-molecule, vacuum-deposited OLEDshaving high efficiency have also been demonstrated with Ir(ppy)₃ as thephosphorescent material and 4,4′-N,N′-dicarbazole-biphenyl (CBP) as thehost (M. A. Baldo, S. Lamansky, P. E. Burrows, M. E. Thompson, S. R.Forrest, Appl. Phys. Lett., 75, 4 (1999), T. Tsutsui, M.-J. Yang, M.Yahiro, K. Nakamura, T. Watanabe, T. Tsuji, Y. Fukuda, T. Wakimoto, S.Miyaguchi, Jpn. J. Appl. Phys., 38, L1502 (1999)).

Another class of phosphorescent materials include compounds havinginteractions between atoms having d¹⁰ electron configuration, such asAu₂(dppm)Cl₂ (dppm=bis(diphenylphosphino)methane) (Y. Ma et al, Appl.Phys. Lett., 74, 1361 (1998)). Still other examples of usefulphosphorescent materials include coordination complexes of the trivalentlanthanides such as Th³⁺ and Eu³⁺ (J. Kido et al, Appl. Phys. Lett., 65,2124 (1994)). While these latter phosphorescent compounds do notnecessarily have triplets as the lowest excited states, their opticaltransitions do involve a change in spin state of 1 and thereby canharvest the triplet excitons in OLED devices.

Although many phosphorescent Ir complexes have been described as usefulin an EL device, Pt-based organometallic complexes have not beenexamined as extensively. Some Pt phosphorescent complexes includecyclometallated Pt(I) complexes such ascis-bis(2-phenylpyridinato-N,C^(2′))platinum(II),cis-bis(2-(2′-thienyl)pyridinato-N,C^(3′)) platinum(II),cis-bis(2-(2′-thienyl)quinolinato-N,C^(5′)) platinum(II), or(2-(4,6-diflourophenyl)pyridinato-NC^(2′)) platinum (II)acetylacetonate. Pt(II) porphyrin complexes such as2,3,7,8,12,13,17,18-octaethyl-21H, 23H-porphine platinum(II) arereported in U.S. Pat. No. 6,048,630 as useful phosphorescent materialsin an electroluminescent device although they did not give a very highluminance yield. Recently, C. Che, W. Lu, and M. Chan reportedorganometallic light-emitting materials based on (C{circumflex over( )}N{circumflex over ( )}N) tridentate cyclometalated Pt(II)arylacetylides. (US 2002/0179885 and references cited therein)

Complexes of a tridentate (N{circumflex over ( )}C{circumflex over( )}N) ligand have been examined, wherein the tridentate (N{circumflexover ( )}C{circumflex over ( )}N) ligand represents a ligand thatcoordinates to the metal through a nitrogen donor bond, a carbon-metalbond, and a nitrogen donor bond, in that order, wherein at least one ofthe nitrogen donors is part of an aromatic ring or an imine group (forexample, see D. Cardenas, A. Echavarren, A. M. Ramirez de Arellano,Organometallics (1999), 18, 3337 (1999) and references cited therein).Nevertheless, there continues a need for additional phosphorescentemitters that exhibit good luminance efficiency in electroluminescentdevices.

SUMMARY OF THE INVENTION

The invention provides an electroluminescent device comprising alight-emitting layer containing a light emitting material that containsan organometallic complex comprising a metal selected from the groupconsisting of Pt, Pd and Ir, and a tridentate (N{circumflex over( )}C{circumflex over ( )}N) ligand, wherein the tridentate(N{circumflex over ( )}C{circumflex over ( )}N) ligand represents aligand that coordinates to the metal through a nitrogen donor bond, acarbon-metal bond, and a nitrogen donor bond, in that order, wherein atleast one of the nitrogen donors is part of an aromatic ring or an iminegroup. The invention also includes a display or room lighting deviceemploying the device of the invention.

The device of the invention provides good luminance efficiency.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a cross-section of a typical OLED device in which thisinvention may be used.

DETAILED DESCRIPTION OF THE INVENTION

The invention is generally summarized above. The organometallic complexof the invention comprises a metal consisting of Pt, Pd or Ir; moredesirably the metal is Pt. The metal forms a complex with a tridentate(N{circumflex over ( )}C{circumflex over ( )}N) ligand, wherein thetridentate (N{circumflex over ( )}C{circumflex over ( )}N) ligandrepresents a ligand that coordinates to the metal through a nitrogendonor bond, a carbon bond, and a nitrogen donor bond, in that order,wherein at least one of the nitrogen donors is part of an aromatic ringor an imine group. The complex may be present in a compound containingtwo or more complexes. Examples of suitable ligands are shown below.Desirably, both of the nitrogen donors are part of an aromatic ring.

In one suitable embodiment, the tridentate organometallic complex can beincorporated into a polymer light emitting diode (PLED) device. Forexample, the organometallic complex can be part of the main chain of apolymer, the side chain, or intermixed with a polymer in such a device.

In one desirable embodiment the organometallic complex can berepresented by Formula (1a),

wherein:

-   -   Ar^(a), Ar^(b), and Ar^(c) independently represent the atoms        necessary to form a five or six-membered aromatic ring, which        may be further substituted including substitution by fused        rings. The term ‘aromatic rings’ includes aromatic rings that        have heteroatoms present in the ring, see for example, J. March,        Advanced Organic Chemistry, Chapter 2 (1985, publisher John        Wiley & Sons, New York, N.Y.). For example, Ar^(b) can represent        the atoms necessary to form groups such as benzene ring groups,        thiophene ring groups, or furan ring groups. Likewise, Ar^(a)        and Ar^(c) can represent the atoms necessary to form groups such        as pyridine ring groups, quinoline ring groups, isoquinoline        ring groups, and indole ring groups as examples. In one        desirable embodiment, Ar^(b) represents a benzene ring group and        Ar^(a) and Ar^(c) independently represent pyridine ring groups.

L represents an anionic ligand having a negative charge and formed byloss of hydrogen from the parent compound LH. In the L-metal bond, moreof the electron density is localized on L, the ligand. For example, Lcan represent halogen, that is fluoride, chloride, bromide, or iodide. Lcan also be chosen so that it forms a carbon-metal bond in theorganometallic complex, for example, L can represent a cyanide, analkynyl group, an alkenyl group, an aryl group, or an alkyl group.Illustrative examples of such L groups are shown below.

L can also represent RX, wherein X forms a bond to the metal (Pt, Pd orIr) and wherein X represents N, O, S, or Se, and R represents asubstituent. For example, R can represent an aryl group or an alkylgroup or a carbonyl group or sulfonyl group. Suitable examples of groupsrepresented by RX are a thiocyanate, alkoxide or aryloxide groups, alkylsulfide or aryl sulfide groups, a carboxlate group or sulfonate group,for example, acetate, trifluoroacetate, tosylate, triflate. Illustrativeexamples of RX are also given below.

In one desirable embodiment the organometallic complex of the inventioncan be represented by Formula (1b).

Z¹-Z¹¹ of formula (1b) represent hydrogen or independently selectedsubstituent groups, provided that adjacent substituent groups cancombine to form rings. Examples of substituents are phenyl groups, alkylgroups such as methyl groups or t-butyl groups. Z⁴ and Z⁵ as well as Z⁷and Z⁸ can also combine to form rings, for example, a 6-memberedsaturated ring or a 6-membered aromatic ring. L represents ian anionicligand.

In another desirable embodiment the organometallic complex can berepresented by Formula (1c).

As described above, Z¹-Z¹¹ represent hydrogen or independently selectedsubstituent groups, provided that adjacent substituent groups cancombine to form rings, and provided that Z⁴ and Z⁵ as well as Z⁷ and Z⁸can combine to form rings. L represents is an anionic ligand.

R¹-R⁵ represent hydrogen or independently selected substituents,provided that adjacent substituents may combine to form a ring group,which may be further substituted including substitution by fused rings.For example, R¹ and R³ can independently represent groups such as methylgroups or isopropyl groups. R¹ and R², and R³ and R⁴ can combine to formrings such as benzene ring groups or tolyl ring groups.

Synthetic Method

Synthesis of the emitting materials useful in the invention may beaccomplished by preparing the organic ligand and then using a metal tocomplex the ligand and form the organometallic compound. Suitabletridentate ligands and their metal complexes can be prepared by variousliterature methods, for example, see M. Beley, J. Collin, J. Sauvage,Inorg. Chem., 32, 4539(1993), M. Beley, J. Collin, R. Louis,B. Metz, J.Sauvage, J. Am. Chem. Soc., 113, 8521 (1991), D. Cardenas, A.Echavarren, Antonio M.; Ramirez de Arellano, M. Carmen, Organometallics,18, 3337 (1999), and M. Sindkhedkar, H. Mulla, M. Wurth, A.Cammers-Goodwin, Tetrahedron, 57, 2991(2001). For example, one syntheticmethod involves reaction of a bromo compound (Rxn-1, wherein Ar^(w)represents the atoms necessary to complete a five or six-memberedaromatic ring group) with butyllithium at low temperature, followed byaddition of zinc chloride. This affords a zinc intermediate. Thisintermediate need not be isolated; after addition oftetrakis(triphenylphosphine)palladium, it can be reacted further with0.5 equivalents of a dibromo compound to afford a tridentate ligand(Rxn-2, wherein Ar^(y) represents the atoms necessary to complete a fiveor six-membered aromatic ring group). Alternatively, two equivalents ofa bromoheterocyclic compound can be reacted with a diboron intermediateto afford a tridentate ligand (Rxn-3). Unsymmetrical ligands can be madeby reacting one equivalent of a bromoheterocyclic compound with adiboron intermediate to afford a bidentate ligand and this ligand can beisolated and then reacted further with another bromoheterocycliccompound to obtain the tridentate ligand (Rxn-4 and Rxn-5, whereinAr^(z) represents the atoms necessary to complete a five or six-memberedaromatic ring group). The ligands can be isolated and purified byvarious methods, including column chromatography.

Reaction of the tridentate ligand with a metal salt, for examplepotassium tetrachloroplatinate, affords the desired organometalliccomplex (Rxn-6). The chloro group in the organometallic complex can bereplaced by other ligands. For example, chloride can be replaced byreaction of the complex with an aryl lithium or zinc salt or a coppercatalyzed reaction with an acetlylene substituted group (Rxn-7 andRxn-8, wherein Ar^(s) represents a five or six-membered aromatic ringgroup, R^(w) is a substituent group).

Illustrative examples of complexes of Formula (1) useful in the presentinvention are the following:

Unless otherwise specifically stated, use of the term “substituted” or“substituent” means any group or atom other than hydrogen. Unlessotherwise provided, when a group (including a compound or complex)containing a substitutable hydrogen is referred to, it is also intendedto encompass not only the unsubstituted form, but also form furthersubstituted derivatives with any substituent group or groups as hereinmentioned, so long as the substituent does not destroy propertiesnecessary for utility. Suitably, a substituent group may be halogen ormay be bonded to the remainder of the molecule by an atom of carbon,silicon, oxygen, nitrogen, phosphorous, sulfur, selenium, or boron. Thesubstituent may be, for example, halogen, such as chloro, bromo orfluoro; nitro; hydroxyl; cyano; carboxyl; or groups which may be furthersubstituted, such as alkyl, including straight or branched chain orcyclic alkyl, such as methyl, trifluoromethyl, ethyl, t-butyl,3-(2,4-di-t-pentylphenoxy)propyl, and tetradecyl; alkenyl, such asethylene, 2-butene; alkoxy, such as methoxy, ethoxy, propoxy, butoxy,2-methoxyethoxy, sec-butoxy, hexyloxy, 2-ethylhexyloxy, tetradecyloxy,2-(2,4-di-t-pentylphenoxy)ethoxy, and 2-dodecyloxyethoxy; aryl such asphenyl, 4-t-butylphenyl, 2,4,6-trimethylphenyl, naphthyl; aryloxy, suchas phenoxy, 2-methylphenoxy, alpha- or beta-naphthyloxy, and 4-tolyloxy;carbonamido, such as acetamido, benzamido, butyramido, tetradecanamido,alpha-(2,4-di-t-pentyl-phenoxy)acetamido,alpha-(2,4-di-t-pentylphenoxy)butyramido,alpha-(3-pentadecylphenoxy)-hexanamido,alpha-(4-hydroxy-3-t-butylphenoxy)-tetradecanamido,2-oxo-pyrrolidin-1-yl, 2-oxo-5-tetradecylpyrrolin-1-yl,N-methyltetradecanamido, N-succinimido, N-phthalimido,2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-imidazolyl, andN-acetyl-N-dodecylamino, ethoxycarbonylamino, phenoxycarbonylamino,benzyloxycarbonylamino, hexadecyloxycarbonylamino,2,4-di-t-butylphenoxycarbonylamino, phenylcarbonylamino,2,5-(di-t-pentylphenyl)carbonylamino, p-dodecyl-phenylcarbonylamino,p-tolylcarbonylamino, N-methylureido, N,N-dimethylureido,N-methyl-N-dodecylureido, N-hexadecylureido, N,N-dioctadecylureido,N,N-dioctyl-N′-ethylureido, N-phenylureido, N,N-diphenylureido,N-phenyl-N-p-tolylureido, N-(m-hexadecylphenyl)ureido,N,N-(2,5-di-t-pentylphenyl)-N′-ethylureido, and t-butylcarbonamido;sulfonamido, such as methylsulfonamido, benzenesulfonamido,p-tolylsulfonamido, p-dodecylbenzenesulfonamido,N-methyltetradecylsulfonamido, N,N-dipropyl-sulfamoylamino, andhexadecylsulfonamido; sulfamoyl, such as N-inethylsulfamoyl,N-ethylsulfamoyl, N,N-dipropylsulfamoyl, N-hexadecylsulfamoyl,N,N-dimethylsulfamoyl, N-[3-(dodecyloxy)propyl]sulfamoyl,N-[4-(2,4-di-t-pentylphenoxy)butyl]sulfamoyl,N-methyl-N-tetradecylsulfamoyl, and N-dodecylsulfamoyl; carbamoyl, suchas N-methylcarbamoyl, N,N-dibutylcarbamoyl, N-octadecylcarbamoyl,N-[4-(2,4-di-t-pentylphenoxy)butyl]carbamoyl,N-methyl-N-tetradecylcarbamoyl, and N,N-dioctylcarbamoyl; acyl, such asacetyl, (2,4-di-t-amylphenoxy)acetyl, phenoxycarbonyl,p-dodecyloxyphenoxycarbonyl methoxycarbonyl, butoxycarbonyl,tetradecyloxycarbonyl, ethoxycarbonyl, benzyloxycarbonyl,3-pentadecyloxycarbonyl, and dodecyloxycarbonyl; sulfonyl, such asmethoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl,2-ethylhexyloxysulfonyl, phenoxysulfonyl,2,4-di-t-pentylphenoxysulfonyl, methylsulfonyl, octylsulfonyl,2-ethylhexylsulfonyl, dodecylsulfonyl, hexadecylsulfonyl,phenylsulfonyl, 4-nonylphenylsulfonyl, and p-tolylsulfonyl; sulfonyloxy,such as dodecylsulfonyloxy, and hexadecylsulfonyloxy; sulfinyl, such asmethylsulfinyl, octylsulfinyl, 2-ethylhexylsulfinyl, dodecylsulfinyl,hexadecylsulfinyl, phenylsulfinyl, 4-nonylphenylsulfinyl, andp-tolylsulfinyl; thio, such as ethylthio, octylthio, benzylthio,tetradecylthio, 2-(2,4-di-t-pentylphenoxy)ethylthio, phenylthio,2-butoxy-5-t-octylphenylthio, and p-tolylthio; acyloxy, such asacetyloxy, benzoyloxy, octadecanoyloxy, p-dodecylamidobenzoyloxy,N-phenylcarbamoyloxy, N-ethylcarbamoyloxy, and cyclohexylcarbonyloxy;amine, such as phenylanilino, 2-chloroanilino, diethylamine,dodecylamine; imino, such as 1 (N-phenylimido)ethyl, N-succinimido or3-benzylhydantoinyl; phosphate, such as dimethylphosphate andethylbutylphosphate; phosphite, such as diethyl and dihexylphosphite; aheterocyclic group, a heterocyclic oxy group or a heterocyclic thiogroup, each of which may be substituted and which contain a 3 to 7membered heterocyclic ring composed of carbon atoms and at least onehetero atom selected from the group consisting of oxygen, nitrogen,sulfur, phosphorous, or boron such as 2-furyl, 2-thienyl,2-benzimidazolyloxy or 2-benzothiazolyl; quaternary ammonium, such astriethylammonium; quaternary phosphonium, such as triphenylphosphonium;and silyloxy, such as trimethylsilyloxy.

If desired, the substituents may themselves be further substituted oneor more times with the described substituent groups. The particularsubstituents used may be selected by those skilled in the art to attainthe desired desirable properties for a specific application and caninclude, for example, electron-withdrawing groups, electron-donatinggroups, and steric groups. When a molecule may have two or moresubstituents, the substituents may be joined together to form a ringsuch as a fused ring unless otherwise provided. Generally, the abovegroups and substituents thereof may include those having up to 48 carbonatoms, typically 1 to 36 carbon atoms and usually less than 24 carbonatoms, but greater numbers are possible depending on the particularsubstituents selected.

Suitably, the light-emitting layer of the OLED device comprises a hostmaterial and one or more guest materials for emitting light. At leastone of the guest materials is suitably a phosphorescent complexcomprising a ring system of Formula 1a. The light-emitting guestmaterial(s) is usually present in an amount less than the amount of hostmaterials and is typically present in an amount of up to 15 wt % ofthehost, more typically from 0.1-10.0 wt % ofthe host For convenience, thephosphorescent complex guest material may be referred to herein as aphosphorescent material. The phosphorescent material of Formula 1a ispreferably a low molecular weight compound, but it may also be anoligomer or a polymer having a main chain or a side chain of repeatingunits having the moiety represented by Formula 1a. It may be provided asa discrete material dispersed in the host material, or it may be bondedin some way to the host material, for example, covalently bonded into apolymeric host.

Host Materials for Phosphorescent Materials

Suitable host materials should be selected so that the triplet excitoncan be transferred efficiently from the host material to thephosphorescent material. For this transfer to occur, it is a highlydesirable condition that the excited state energy of the phosphorescentmaterial be lower than the difference in energy between the lowesttriplet state and the ground state of the host. However, the band gap ofthe host should not be chosen so large as to cause an unacceptableincrease in the drive voltage of the OLED. Suitable host materials aredescribed in WO 00/70655 A2; 01/39234 A2; 01/93642 A1; 02/074015 A2;02/15645 A1, and US 20020117662. Suitable hosts include certain arylamines, triazoles, indoles and carbazole compounds. Examples ofdesirable hosts are 4,4′-N,N′-dicarbazole-biphenyl (CBP),2,2′-dimethyl-4,4′-N,N′-dicarbazole-biphenyl,m-(N,N′-dicarbazole)benzene, and poly(N-vinylcarbazole), including theirderivatives.

Desirable host materials are capable of forming a continuous film. Thelight-emitting layer may contain more than one host material in order toimprove the device's film morphology, electrical properties, lightemission efficiency, and lifetime. The light emitting layer may containa first host material that has good hole-transporting properties, and asecond host material that has good electron-transporting properties.

Other Phosphorescent Materials

Phosphorescent materials of Formula 1a may be used in combination withother phosphorescent materials, either in the same or different layers.Some other phosphorescent materials are described in WO 00/57676, WO00/70655, WO 01/41512 A1, WO 02/15645 A1, US 2003/0017361 A1, WO01/93642 A1, WO 01/39234 A2, U.S. Pat. No. 6,458,475 B1, WO 02/071813A1, U.S. Pat. No. 6,573,651 B2, US 2002/0197511 A1, WO 02/074015 A2,U.S. Pat. No. 6,451,455 B1, US 2003/0072964 A1, US 2003/0068528 A1, U.S.Pat. No. 6,413,656 B1, U.S. Pat. No. 6,515,298 B2, U.S. Pat. No.6,451,415 B1, U.S. Pat. No. 6,097,147, US 2003/0124381 A1, US2003/0059646 A1, US 2003/0054198 A1, EP 1 239 526 A2, EP 1 238 981 A2,EP 1 244 155 A2, US 2002/0100906 A1, US 2003/0068526 A1, US 2003/0068535A1, JP 2003073387A, JP 2003 073388A, US 2003/0141809 A1, US 2003/0040627A1, JP 2003059667A, JP 2003073665A, and US 2002/0121638 A1.

The emission wavelengths of cyclometallated Ir(III) complexes of thetype IrL₃ and IrL₂L′, such as the green-emittingfac-tris(2-phenylpyridinato-N,C^(2′))Iridium(IR) andbis(2-phenylpyridinato-N,C^(2′))Iridium(III)(acetylacetonate) may beshifted by substitution of electron donating or withdrawing groups atappropriate positions on the cyclometallating ligand L, or by choice ofdifferent heterocycles for the cyclometallating ligand L. The emissionwavelengths may also be shifted by choice of the ancillary ligand L′.Examples of red emitters are thebis(2-(2′-benzothienyl)pyridinato-N,C^(3′))Iridium(III)(acetylacetonate)and tris(1-phenylisoquinolinato-N,C)Iridium(H). A blue-emitting exampleisbis(2-(4,6-diflourophenyl)-pyridinato-N,C^(2′))Iridium(II)(picolinate).

Red electrophosphorescence has been reported, usingbis(2-(2′-benzo[4,5-a)thienyl)pyridinato-N,C³) iridium (acetylacetonate)[Btp₂Ir(acac)] as the phosphorescent material (Adachi, C., Lamansky, S.,Baldo, M. A., Kwong, R. C., Thompson, M. E., and Forrest, S. R., App.Phys. Lett., 78, 1622-1624 (2001).

Still other examples of useful phosphorescent materials includecoordination complexes of the trivalent lanthanides such as Tb³⁺ andEu³⁺ (J. Kido et al, Appl. Phys. Lett., 65, 2124 (1994))

Blocking Layers

In addition to suitable hosts, an OLED device employing a phosphorescentmaterial often requires at least one exciton or hole blocking layers tohelp confine the excitons or electron-hole recombination centers to thelight-emitting layer comprising the host and phosphorescent material. Inone embodiment, such a blocking layer would be placed between theelectron-transporting layer and the light-emitting layer—see FIG. 1,layer 110. In this case, the ionization potential of the blocking layershould be such that there is an energy barrier for hole migration fromthe host into the electron-transporting layer, while the electronaffinity should be such that electrons pass more readily from theelectron-transporting layer into the light-emitting layer comprisinghost and phosphorescent material. It is further desired, but notabsolutely required, that the triplet energy of the blocking material begreater than that of the phosphorescent material. Suitable hole-blockingmaterials are described in WO 00/70655A2 and WO 01/93642 A1. Twoexamples of useful materials are bathocuproine (BCP) andbis(2-methyl-8-quinolinolato)(4-phenylphenolato)Aluminum(Ill) (BAlQ).Metal complexes other than Balq are also known to block holes andexcitons as described in US 20030068528. US 20030175553 A1 describes theuse of fac-tris(1-phenylpyrazolato-N,C2)iridium(III) (Irppz) in anelectron/exciton blocking layer.

Embodiments of the invention can provide advantageous features such asoperating efficiency, higher luminance, color hue, low drive voltage,and improved operating stability. Embodiments of the organometalliccompounds useful in the invention can provide a wide range of huesincluding those useful in the emission of white light (directly orthrough filters to provide multicolor displays).

General Device Architecture

The present invention can be employed in many OLED device configurationsusing small molecule materials, oligomeric materials, polymericmaterials, or combinations thereof. These include very simple structurescomprising a single anode and cathode to more complex devices, such aspassive matrix displays comprised of orthogonal arrays of anodes andcathodes to form pixels, and active-matrix displays where each pixel iscontrolled independently, for example, with thin film transistors(TFTs).

There are numerous configurations of the organic layers wherein thepresent invention can be successfully practiced. The essentialrequirements of an OLED are an anode, a cathode, and an organiclight-emitting layer located between the anode and cathode. Additionallayers may be employed as more fully described hereafter.

A typical structure, especially useful for of a small molecule device,is shown in FIG. 1 and is comprised of a substrate 101, an anode 103, ahole-injecting layer 105, a hole-transporting layer 107, alight-emitting layer 109, a hole- or exciton-blocking layer 110, anelectron-transporting layer 111, and a cathode 113. These layers aredescribed in detail below. Note that the substrate may alternatively belocated adjacent to the cathode, or the substrate may actuallyconstitute the anode or cathode. The organic layers between the anodeand cathode are conveniently referred to as the organic EL element.Also, the total combined thickness of the organic layers is desirablyless than 500 nm.

The anode and cathode of the OLED are connected to a voltage/currentsource through electrical conductors. The OLED is operated by applying apotential between the anode and cathode such that the anode is at a morepositive potential than the cathode. Holes are injected into the organicEL element from the anode and electrons are injected into the organic ELelement at the cathode. Enhanced device stability can sometimes beachieved when the OLED is operated in an AC mode where, for some timeperiod in the cycle, the potential bias is reversed and no currentflows. An example of an AC driven OLED is described in U.S. Pat. No.5,552,678.

Substrate

The OLED device of this invention is typically provided over asupporting substrate 101 where either the cathode or anode can be incontact with the substrate. The electrode in contact with the substrateis conveniently referred to as the bottom electrode. Conventionally, thebottom electrode is the anode, but this invention is not limited to thatconfiguration. The substrate can either be light transmissive or opaque,depending on the intended direction of light emission. The lighttransmissive property is desirable for viewing the EL emission throughthe substrate. Transparent glass or plastic is commonly employed in suchcases. The substrate can be a complex structure comprising multiplelayers of materials. This is typically the case for active matrixsubstrates wherein TFTs are provided below the OLED layers. It is stillnecessary that the substrate, at least in the emissive pixilated areas,be comprised of largely transparent materials such as glass or polymers.For applications where the EL emission is viewed through the topelectrode, the transmissive characteristic of the bottom support isimmaterial, and therefore can be light transmissive, light absorbing orlight reflective. Substrates for use in this case include, but are notlimited to, glass, plastic, semiconductor materials, silicon, ceramics,and circuit board materials. Again, the substrate can be a complexstructure comprising multiple layers of materials such as found inactive matrix TFT designs. It is necessary to provide in these deviceconfigurations a light-transparent top electrode.

Anode

When the desired electroluminescent light emission (EL) is viewedthrough the anode, the anode should be transparent or substantiallytransparent to the emission of interest. Common transparent anodematerials used in this invention are indium-tin oxide (ITO), indium-zincoxide (IZO) and tin oxide, but other metal oxides can work including,but not limited to, aluminum- or indium-doped zinc oxide,magnesium-indium oxide, and nickel-tungsten oxide. In addition to theseoxides, metal nitrides, such as gallium nitride, and metal selenides,such as zinc selenide, and metal sulfides, such as zinc sulfide, can beused as the anode. For applications where EL emission is viewed onlythrough the cathode, the transmissive characteristics of the anode areimmaterial and any conductive material can be used, transparent, opaqueor reflective. Example conductors for this application include, but arenot limited to, gold, iridium, molybdenum, palladium, and platinum.Typical anode materials, transmissive or otherwise, have a work functionof 4.1 eV or greater. Desired anode materials are commonly deposited byany suitable means such as evaporation, sputtering, chemical vapordeposition, or electrochemical means. Anodes can be patterned usingwell-known photolithographic processes. Optionally, anodes may bepolished prior to application of other layers to reduce surfaceroughness so as to minimize shorts or enhance reflectivity.

Cathode

When light emission is viewed solely through the anode, the cathode usedin this invention can be comprised of nearly any conductive material.Desirable materials have good film-forming properties to ensure goodcontact with the underlying organic layer, promote electron injection atlow voltage, and have good stability. Useful cathode materials oftencontain a low work function metal (<4.0 eV) or metal alloy. One usefulcathode material is comprised of a Mg:Ag alloy wherein the percentage ofsilver is in the range of 1 to 20%, as described in U.S. Pat. No.4,885,221. Another suitable class of cathode materials includes bilayerscomprising the cathode and a thin electron-injection layer (EL) incontact with an organic layer (e.g., an electron transporting layer(ETL)) which is capped with a thicker layer of a conductive metal. Here,the EIL preferably includes a low work function metal or metal salt, andif so, the thicker capping layer does not need to have a low workfunction. One such cathode is comprised of a thin layer of LiF followedby a thicker layer of Al as described in U.S. Pat. No. 5,677,572. An ETLmaterial doped with an alkali metal, for example, Li-doped Alq, isanother example of a useful EIL. Other useful cathode material setsinclude, but are not limited to, those disclosed in U.S. Pat. Nos.5,059,861, 5,059,862, and 6,140,763.

When light emission is viewed through the cathode, the cathode must betransparent or nearly transparent. For such applications, metals must bethin or one must use transparent conductive oxides, or a combination ofthese materials. Optically transparent cathodes have been described inmore detail in U.S. Pat. No. 4,885,211, U.S. Pat. No. 5,247,190, JP3,234,963, U.S. Pat. No. 5,703,436, U.S. Pat. No. 5,608,287, U.S. Pat.No. 5,837,391, U.S. Pat. No. 5,677,572, U.S. Pat. No. 5,776,622, U.S.Pat. No. 5,776,623, U.S. Pat. No. 5,714,838, U.S. Pat. No. 5,969,474,U.S. Pat. No. 5,739,545, U.S. Pat. No. 5,981,306, U.S. Pat. No.6,137,223, U.S. Pat. No. 6,140,763, U.S. Pat. No. 6,172,459, EP 1 076368, U.S. Pat. No. 6,278,236, and U.S. Pat. No. 6,284,3936. Cathodematerials are typically deposited by any suitable method such asevaporation, sputtering, or chemical vapor deposition. When needed,patterning can be achieved through many well known methods including,but not limited to, through-mask deposition, integral shadow masking asdescribed in U.S. Pat. No. 5,276,380 and EP 0 732 868, laser ablation,and selective chemical vapor deposition.

Hole-Injecting Layer (HIL)

A hole-injecting layer 105 may be provided between anode 103 andhole-transporting layer 107. The hole-injecting material can serve toimprove the film formation property of subsequent organic layers and tofacilitate injection of holes into the hole-transporting layer. Suitablematerials for use in the hole-injecting layer include, but are notlimited to, porphyrinic compounds as described in U.S. Pat. No.4,720,432, plasma-deposited fluorocarbon polymers as described in U.S.Pat. No. 6,208,075, and some aromatic amines, for example, m-MTDATA(4,4′,4″-tris[(3-methylphenyl)phenylamino]triphenylamine). Alternativehole-injecting materials reportedly useful in organic EL devices aredescribed in EP 0 891 121 A1 and EP 1 029 909 A1.

Hole-Transporting Layer (HTL)

The hole-transporting layer 107 of the organic EL device contains atleast one hole-transporting compound such as an aromatic tertiary amine,where the latter is understood to be a compound containing at least onetrivalent nitrogen atom that is bonded only to carbon atoms, at leastone of which is a member of an aromatic ring. In one form the aromatictertiary amine can be an arylamine, such as a monoarylamine,diarylamine, triarylamine, or a polymeric arylamine. Exemplary monomerictriarylamines are illustrated by Klupfel et al. U.S. Pat. No. 3,180,730.Other suitable-triarylamines substituted with one or more vinyl radicalsand/or comprising at least one active hydrogen containing group aredisclosed by Brantley et al U.S. Pat. No. 3,567,450 and U.S. Pat. No.3,658,520.

A more preferred class of aromatic tertiary amines are those whichinclude at least two aromatic tertiary amine moieties as described inU.S. Pat. No. 4,720,432 and U.S. Pat. No. 5,061,569. Such compoundsinclude those represented by structural formula (A).

wherein Q₁ and Q₂ are independently selected aromatic tertiary aminemoieties 5 and G is a linking group such as an arylene, cycloalkylene,or alkylene group of a carbon to carbon bond. In one embodiment, atleast one of Q₁ or Q₂ contains a polycyclic fused ring structure, e.g.,a naphthalene. When G is an aryl group, it is conveniently a phenylene,biphenylene, or naphthalene moiety.

A useful class of triarylamines satisfying structural formula (A) and locontaining two triarylamine moieties is represented by structuralformula (B):

where

-   -   R₁ and R₂ each independently represents a hydrogen atom, an aryl        group, or an alkyl group or R₁ and R₂ together represent the        atoms completing a cycloalkyl group; and    -   R₃ and R₄ each independently represents an aryl group, which is        in turn substituted with-a diaryl substituted amino group, as        indicated by structural formula (C):        wherein R₅ and R₆ are independently selected aryl groups. In one        embodiment, at least one of R₅ or R₆ contains a polycyclic fused        ring structure, e.g., a naphthalene.

Another class of aromatic tertiary amines are the tetraaryldiamines.Desirable tetraaryldiamines include two diarylamino groups, such asindicated by formula (C), linked through an arylene group. Usefultetraaryldiamines include those represented by formula (D).

wherein

-   -   each Are is an independently selected arylene group, such as a        phenylene or anthracene moiety,    -   n is an integer of from 1 to 4, and    -   Ar, R₇, R_(8,) and R₉ are independently selected aryl groups.

In a typical embodiment, at least one of Ar, R₇, R_(8,) and R₉ is apolycyclic fused ring structure, e.g., a naphthalene

The various alkyl, alkylene, aryl, and arylene moieties of the foregoingstructural formulae (A), (B), (C), (D), can each in turn be substituted.Typical substituents include alkyl groups, alkoxy groups, aryl groups,aryloxy groups, and halogen such as fluoride, chloride, and bromide. Thevarious alkyl and alkylene moieties typically contain from about 1 to 6carbon atoms. The cycloalkyl moieties can contain from 3 to about 10carbon atoms, but typically contain five, six, or seven ring carbonatoms—e.g., cyclopentyl, cyclohexyl, and cycloheptyl ring structures.The aryl and arylene moieties are usually phenyl and phenylene moieties.

The hole-transporting layer can be formed of a single or a mixture ofaromatic tertiary amine compounds. Specifically, one may employ atriarylamine, such as a triarylamine satisfying the formula (B), incombination with a tetraaryldiamine, such as indicated by formula (D).When a triarylamine is employed in combination with a tetraaryldiamine,the latter is positioned as a layer interposed between the triarylamineand the electron injecting and transporting layer. Illustrative ofuseful aromatic tertiary amines are the following:

-   -   1,1-Bis(4-di-p-tolylaminophenyl)cyclohexane    -   1,1-Bis(4-di-p-tolylaminophenyl)-4-phenylcyclohexane    -   N,N,N′,N′-tetraphenyl-4,4′″-diamino-1,1′:4′,1″:4″,1′″-quaterphenyl    -   Bis(4-dimethylamino-2-methylphenyl)phenylmethane    -   1,4-bis[2-[4-[N,N-di(p-toly)amino]phenyl]vinyl]benzene (BDTAPVB)    -   N,N,N′,N′-Tetra-p-tolyl-4,4′-diaminobiphenyl    -   N,N,N′,N′-Tetraphenyl-4,4′-diaminobiphenyl    -   N,N,N′,N′-tetra-1-naphthyl-4,4′-diaminobiphenyl    -   N,N,N′,N′-tetra-2-naphthyl-4,4′-diaminobiphenyl    -   N-Phenylcarbazole    -   4,4′-Bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB)    -   4,4′-Bis[N-(1-naphthyl)-N-(2-naphthyl)amino]biphenyl (TNB)    -   4,4′-Bis[N-(1-naphthyl)-N-phenylamino]p-terphenyl    -   4,4′-Bis[N-(2-naphthyl)-N-phenylamino]biphenyl    -   4,4′-Bis[N-(3-acenaphthenyl)-N-phenylamino]biphenyl    -   1,5-Bis[N-(1-naphthyl)-N-phenylamino]naphthalene    -   4,4′-Bis[N-(9-anthryl)-N-phenylamino]biphenyl    -   4,4′-Bis[N-(1-anthryl)-N-phenylamino]-p-terphenyl    -   4,4′-Bis[N-(2-phenanthryl)-N-phenylamino]biphenyl    -   4,4′-Bis[N-(8-fluoranthenyl)-N-phenylamino]biphenyl    -   4,4′-Bis[N-(2-pyrenyl)-N-phenylamino]biphenyl    -   4,4′-Bis[N-(2-naphthacenyl)-N-phenylamino]biphenyl    -   4,4′-Bis[N-(2-perylenyl)-N-phenylamino]biphenyl    -   4,4′-Bis[N-(1-coronenyl)-N-phenylamino]biphenyl    -   2,6-Bis(di-p-tolylamino)naphthalene    -   2,6-Bis[di-(1-naphthyl)amino]naphthalene    -   2,6-Bis[N-(1-naphthyl)-N-(2-naphthyl)amino]naphthalene    -   N,N,N′,N′-Tetra(2-naphthyl)-4,4″-diamino-p-terphenyl    -   4,4′-Bis{N-phenyl-N-[4-(1-naphthyl)-phenyl]amino}biphenyl    -   2,6-Bis[N,N-di(2-naphthyl)amino]fluorene    -   4,4′,4″-tris[(3-methylphenyl)phenylamino]triphenylamine (MTDATA)    -   4,4′-Bis[N-(3-methylphenyl)-N-phenylamino]biphenyl (TPD)

Another class of useful hole-transporting materials includes polycyclicaromatic compounds as described in EP 1 009 041. Tertiary aromaticamines with more than two amine groups may be used including oligomericmaterials. In addition, polymeric hole-transporting materials can beused such as poly(N-vinylcarbazole) (PVK), polythiophenes, polypyrrole,polyaniline, and copolymers such aspoly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) also calledPEDOT/PSS.

Fluorescent Light-Emitting Materials and Layers (LEL)

In addition to the phosphorescent materials of this invention, otherlight emitting materials may be used in the OLED device, includingfluorescent materials. Although the term “fluorescent” is commonly usedto describe any light emitting material, in this case we are referringto a material that emits light from a singlet excited state. Fluorescentmaterials may be used in the same layer as the phosphorescent material,in adjacent layers, in adjacent pixels, or any combination. Care must betaken not to select materials that will adversely affect the performanceof the phosphorescent materials of this invention. One skilled in theart will understand that triplet excited state energies of materials inthe same layer as the phosphorescent material or in an adjacent layermust be appropriately set so as to prevent unwanted quenching.

As more fully described in U.S. Pat. Nos. 4,769,292 and 5,935,721, thelight-emitting layer (LEL) of the organic EL element includes aluminescent fluorescent or phosphorescent material whereelectroluminescence is produced as a result of electron-hole pairrecombination in this region. The light-emitting layer can be comprisedof a single material, but more commonly consists of a host materialdoped with a guest emitting material or materials where light emissioncomes primarily from the emitting materials and can be of any color. Thehost materials in the light-emitting layer can be anelectron-transporting material, as defined below, a hole-transportingmaterial, as defined above, or another material or combination ofmaterials that support hole-electron recombination. Fluorescent emittingmaterials are typically incorporated at 0.01 to 10% by weight of thehost material.

The host and emitting materials can be small non-polymeric molecules orpolymeric materials such as polyfluorenes and polyvinylarylenes (e.g.,poly(p-phenylenevinylene), PPV). In the case of polymers, small moleculeemitting materials can be molecularly dispersed into a polymeric host,or the emitting materials can be added by copolymerizing a minorconstituent into a host polymer. Host materials may be mixed together inorder to improve film formation, electrical properties, light emissionefficiency, lifetime, or manufacturability. The host may comprise amaterial that has good hole-transporting properties and a material thathas good electron-transporting properties.

An important relationship for choosing a fluorescent dye as a guestemitting material is a comparison of the singlet excited state energiesof the host and light-emitting material. For efficient energy transferfrom the host to the emitting material, a highly desirable condition isthat the singlet excited state energy of the emitting material is lowerthan that of the host material.

Host and emitting materials known to be of use include, but are notlimited to, those disclosed in U.S. Pat. No. 4,768,292, U.S. Pat. No.5,141,671, U.S. Pat. No. 5,150,006, U.S. Pat. No. 5,151,629, U.S. Pat.No. 5,405,709, U.S. Pat. No. 5,484,922, U.S. Pat. No. 5,593,788, U.S.Pat. No. 5,645,948, U.S. Pat. No. 5,683,823, U.S. Pat. No. 5,755,999,U.S. Pat. No. 5,928,802, U.S. Pat. No. 5,935,720, U.S. Pat. No.5,935,721, and U.S. Pat. No. 6,020,078.

Metal complexes of 8-hydroxyquinoline and similar derivatives (FormulaE) constitute one class of useful host compounds capable of supportingelectroluminescence, and are particularly suitable for light emission ofwavelengths longer than 500 nm, e.g., green, yellow, orange, and red.

wherein

-   -   M represents a metal;    -   n is an integer of from 1 to 4; and    -   Z independently in each occurrence represents the atoms        completing a nucleus having at least two fused aromatic rings.

From the foregoing it is apparent that the metal can be monovalent,divalent, trivalent, or tetravalent metal. The metal can, for example,be an alkali metal, such as lithium, sodium, or potassium; an alkalineearth metal, such as magnesium or calcium; an earth metal, such aluminumor gallium, or a transition metal such as zinc or zirconium. Generallyany monovalent, divalent, trivalent, or tetravalent metal known to be auseful chelating metal can be employed.

Z completes a heterocyclic nucleus containing at least two fusedaromatic rings, at least one of which is an azole or azine ring.Additional rings, including both aliphatic and aromatic rings, can befused with the two required rings, if required. To avoid addingmolecular bulk without improving on function the number of ring atoms isusually maintained at 18 or less.

Illustrative of useful chelated oxinoid compounds are the following:

-   -   CO-1: Aluminum trisoxine [alias,        tris(8-quinolinolato)aluminum(III)]    -   CO-2: Magnesium bisoxine [alias,        bis(8-quinolinolato)magnesium(II)]    -   CO-3: Bis[benzo{f}-8-quinolinolato]zinc(II)    -   CO-4:        Bis(2-methyl-8-quinolinolato)aluminum(III)-μ-oxo-bis(2-methyl-8-quinolinolato)aluminum(III)    -   CO-5: Indium trisoxine [alias, tris(8-quinolinolato)indium]    -   CO-6: Aluminum tris(5-methyloxine) [alias,        tris(5-methyl-8-quinolinolato)aluminum(III)]    -   CO-7: Lithium oxine [alias,(8-quinolinolato)lithium(I)]    -   CO-8: Gallium oxine [alias, tris(8-quinolinolato)gallium(III)]    -   CO-9: Zirconium oxine [alias,        tetra(8-quinolinolato)zirconium(IV)]

Derivatives of 9,10-di-(2-naphthyl)anthracene (Formula F) constitute oneclass of useful host materials capable of supportingelectroluminescence, and are particularly suitable for light emission ofwavelengths longer than 400 nm, e.g., blue, green, yellow, orange orred.

wherein: R¹, R², R³, R⁴, R⁵, and R⁶ represent one or more substituentson each ring where each substituent is individually selected from thefollowing groups:

-   -   Group 1: hydrogen, or alkyl of from 1 to 24 carbon atoms;    -   Group 2: aryl or substituted aryl of from 5 to 20 carbon atoms;    -   Group 3: carbon atoms from 4 to 24 necessary to complete a fused        aromatic ring of anthracenyl; pyrenyl, or perylenyl;    -   Group 4: heteroaryl or substituted heteroaryl of from 5 to 24        carbon atoms as necessary to complete a fused heteroaromatic        ring of furyl, thienyl, pyridyl, quinolinyl or other        heterocyclic systems;    -   Group 5: alkoxylamino, alkylamino, or arylamino of from 1 to 24        carbon atoms; and    -   Group 6: fluorine, chlorine, bromine or cyano.

Illustrative examples include 9,10-di-(2-naphthyl)anthracene and2-t-butyl-9,10-di-(2-naphthyl)anthracene. Other anthracene derivativescan be useful as a host in the LEL, including derivatives of9,10-bis[4-(2,2-diphenylethenyl)phenyl]anthracene.

Benzazole derivatives (Formula G) constitute another class of usefulhost materials capable of supporting electroluminescence, and areparticularly suitable for light emission of wavelengths longer than 400nm, e.g., blue, green, yellow, orange or red.

Where:

-   -   n is an integer of 3 to 8;    -   Z is O, NR or S; and    -   R and R¹ are individually hydrogen; alkyl of from 1 to 24 carbon        atoms, for example, propyl, t-butyl, heptyl, and the like; aryl        or hetero-atom substituted aryl of from 5 to 20 carbon atoms for        example phenyl and naphthyl, turyl, thienyl, pyridyl, quinolinyl        and other heterocyclic systems; or halo such as chloro, fluoro;        or atoms necessary to complete a fused aromatic ring; and

L is a linkage unit consisting of alkyl, aryl, substituted alkyl, orsubstituted aryl, which conjugately or unconjugately connects themultiple benzazoles together. An example of a useful benzazole is2,2′,2″-(1,3,5-phenylene)tris[1-phenyl-1H-benzimidazole].

Styrylarylene derivatives as described in U.S. Pat. No. 5,121,029 and JP08333569 are also useful hosts for blue emission. For example,9,10-bis[4-(2,2-diphenylethenyl)phenyl]anthracene and4,4′-Bis(2,2-diphenylethenyl)-1,1′-biphenyl (DPVBi) are useful hosts forblue emission.

Useful fluorescent emitting materials include, but are not limited to,derivatives of anthracene, tetracene, xanthene, perylene, rubrene,coumarin, rhodamine, and quinacridone, dicyanomethylenepyran compounds,thiopyran compounds, polymethine compounds, pyrilium and thiapyriliumcompounds, fluorene derivatives, periflanthene derivatives,indenoperylene derivatives, bis(azinyl)amine boron compounds,bis(azinyl)methane compounds, and carbostyryl compounds. Illustrativeexamples of useful materials include, but are not limited to, thefollowing:

L1

L2

L3

L4

L5

L6

L7

L8

X R1 R2 L9 O H H L10 O H Methyl L11 O Methyl H L12 O Methyl Methyl L13 OH t-butyl L14 O t-butyl H L15 O t-butyl t-butyl L16 S H H L17 S H MethylL18 S Methyl H L19 S Methyl Methyl L20 S H t-butyl L21 S t-butyl H L22 St-butyl t-butyl

X R1 R2 L23 O H H L24 O H Methyl L25 O Methyl H L26 O Methyl Methyl L27O H t-butyl L28 O t-butyl H L29 O t-butyl t-butyl L30 S H H L31 S HMethyl L32 S Methyl H L33 S Methyl Methyl L34 S H t-butyl L35 S t-butylH L36 S t-butyl t-butyl

R L37 phenyl L38 methyl L39 t-butyl L40 mesityl

R L41 phenyl L42 methyl L43 t-butyl L44 mesityl

L45

L46

L47

L48

L49

L50

L51

L52Electron-Transporting Layer (ETL)

Preferred thin film-forming materials for use in forming theelectron-transporting layer 111 of the organic EL devices of thisinvention are metal chelated oxinoid compounds, including chelates ofoxine itself (also commonly referred to as 8-quinolinol or8-hydroxyquinoline). Such compounds help to inject and transportelectrons and exhibit both high levels of performance and are readilyfabricated in the form of thin films. Exemplary of contemplated oxinoidcompounds are those satisfying structural formula (E), previouslydescribed.

Other electron-transporting materials include various butadienederivatives as disclosed in U.S. Pat. No. 4,356,429 and variousheterocyclic optical brighteners as described in U.S. Pat. No.4,539,507. Benzazoles satisfying structural formula (G) are also usefulelectron transporting materials. Triazines are also known to be usefulas electron transporting materials.

Other Useful Organic Layers and Device Architecture

In some instances, layers 109 through 111 can optionally be collapsedinto a single layer that serves the function of supporting both lightemission and electron transportation. Layers 110 and 111 may also becollapsed into a single layer that functions to block holes or excitons,and supports electron transportation. It also known in the art thatemitting materials may be included in the hole-transporting layer, whichmay serve as a host. Multiple materials may be added to one or morelayers in order to create a white-emitting OLED, for example, bycombining blue- and yellow-emitting materials, cyan- and red-emittingmaterials, or red-, green-, and blue-emitting materials. White-emittingdevices are described, for example, in EP 1 187 235, US 20020025419, EP1 182 244, U.S. Pat. No. 5,683,823, U.S. Pat. No. 5,503,910, U.S. Pat.No. 5,405,709, and U.S. Pat. No. 5,283,182 and can be equipped with asuitable filter arrangement to produce a color emission.

This invention may be used in so-called stacked device architecture, forexample, as taught in U.S. Pat. No. 5,703,436 and U.S. Pat. No.6,337,492.

Deposition of Organic Layers

The organic materials mentioned above are suitably deposited by anymeans suitable for the form of the organic materials. In the case ofsmall molecules, they are conveniently deposited through sublimation,but can be deposited by other means such as from a solvent with anoptional binder to improve film formation. If the material is a polymer,solvent deposition is usually preferred. The material to be deposited bysublimation can be vaporized from a sublimator “boat” often comprised ofa tantalum material, e.g., as described in U.S. Pat. No. 6,237,529, orcan be first coated onto a donor sheet and then sublimed in closerproximity to the substrate. Layers with a mixture of materials canutilize separate sublimator boats or the materials can be pre-mixed andcoated from a single boat or donor sheet. Patterned deposition can beachieved using shadow masks, integral shadow masks (U.S. Pat. No.5,294,870), spatially-defined thermal dye transfer from a donor sheet(U.S. Pat. No. 5,688,551, U.S. Pat. No. 5,851,709 and U.S. Pat. No.6,066,357) and inkjet method (U.S. Pat. No. 6,066,357).

Encapsulation

Most OLED devices are sensitive to moisture or oxygen, or both, so theyare commonly sealed in an inert atmosphere such as nitrogen or argon,along with a desiccant such as alumina, bauxite, calcium sulfate, clays,silica gel, zeolites, alkaline metal oxides, alkaline earth metaloxides, sulfates, or metal halides and perchlorates. Methods forencapsulation and desiccation include, but are not limited to, thosedescribed in U.S. Pat. No. 6,226,890. In addition, barrier layers suchas SiOx, Teflon, and alternating inorganic/polymeric layers are known inthe art for encapsulation.

Optical Optimization

OLED devices of this invention can employ various well-known opticaleffects in order to enhance its properties if desired. This includesoptimizing layer thicknesses to yield maximum light transmission,providing dielectric mirror structures, replacing reflective electrodeswith light-absorbing electrodes, providing anti-glare or anti-reflectioncoatings over the display, providing a polarizing medium over thedisplay, or providing colored, neutral density, or color-conversionfilters over the display. Filters, polarizers, and anti-glare oranti-reflection coatings may be specifically provided over the cover oras part of the cover.

The invention and its advantages can be better appreciated by thefollowing examples.

SYNTHETIC EXAMPLE 1

This example illustrates the preparation of the platinum complexes ofthe invention. The tridentate ligand 1,3-di(2-pyridyl)benzene wasprepared by the following procedure. A solution of 2-bromopyridine(12.38 g, 78.4 mmol) in anhydrous THF (100 mL) was cooled with a dryice-acetone bath and was added dropwise to a solution of n-BuLi inhexanes (53.6 mL, 1.6 M, 85.8 mmol) under nitrogen atmosphere. Afteraddition was complete (ca. 30 min), the resultant mixture was stirred at−78 ° C. for 30 min. A solution of ZnCl₂ in Et₂O (50 mL, 1.0 M, 50 mmol,Aldrich) was added slowly into the reaction mixture via syringe (ca. 10min). The dry ice-acetone bath was removed after the addition of ZnCl₂and the mixture was warmed to room temperature. Pd(PPh₃)₄ (1.84 g, 1.6mmol, Aldrich) was added to the reaction mixture and followed by1,3-dibromobenzene (6.14 g, 26 mmol). The mixture was stirred at roomtemperature for 3 h then refluxed for 22 h. After cooling to roomtemperature, the mixture was quenched with MeOH (10 mL). The crudeproduct was purified by repeated chromatography on silica gel withCH₂Cl₂-EtOAc (from 6:1 to 4:1). This afforded 4.78 g of1,3-di(2-pyridyl)benzene, 79% yield; ¹H NMR Spectrum (300 MHz, CDCl₃,TMS): δ 7.1-7.2 (m, 2 H), 7.55 (t, J=7.6 Hz, 1 H), 7.65-7.7 (m, 2H),7.75-8.1 (m, 2 H), 8.65-8.7 (m, 3 H); ¹³C NMR spectrum(75 MHz, CDCl3,TMS): δ 120.42 (2C), 122.01 (2C), 125.25, 127.19 (2C), 128.96, 136.51(2C), 139.59 (2C), 149.37 (2C), 156.84 (2C).

The complex Inv-1 was prepared according to the literature procedure bythe reaction of potassium tetrachloroplatinate with1,3-di(2-pyridyl)benzene in acetic acid at 110-115 ° C. for 3 days (D.Cardenas, A. Echavarren, M. Ramirez de Arellano, Organometallic, 18,3337 (1999)) and purified by flash chromatography on silica gel withCH₂Cl₂-EtOAc (9:1) eluent. A sublimed sample was used for OLED devicepreparation.

The emission spectra of Inv-1 was obtained at room temperature in ethylacetate solution using a procedure well known to those skilled in theart (see, for example, C. A. Parker and W. T. Rees, Analyst, 85, 587(1960)). Compound Inv-1 had a λmax of emission of 488 nm with a quantumyield of 0.271.

DEVICE EXAMPLE 1

An EL device (Sample 1) satisfying the requirements of the invention wasconstructed in the following manner:

-   -   1. A glass substrate coated with an 85 nm layer of indium-tin        oxide (ITO) as the anode was sequentially ultrasonicated in a        commercial detergent, rinsed in deionized water, degreased in        toluene vapor and exposed to oxygen plasma for about 1 min.    -   2. Over the ITO was deposited a 1 nm fluorocarbon (CFx)        hole-injecting layer (HIL) by plasma-assisted deposition of        CHF₃.    -   3. A hole-transporting layer (HTL) of        N,N′-di-1-naphthyl-N,N′-diphenyl-4,4′-diaminobiphenyl (NPB)        having a thickness of 75 nm was then evaporated from a tantalum        boat.    -   4. A 35 nm light-emitting layer (LEL) of        4,4′-N,N′-dicarbazole-byphenyl (CBP) and Inv-1 (2% wt %) were        then deposited onto the hole-transporting layer. These materials        were also evaporated from tantalum boats.    -   5. A hole-blocking layer of bathocuproine (BCP) having a        thickness of 10 nm was then evaporated from a tantalum boat.    -   6. A 40 nm electron-transporting layer (ETL) of        tris(8-quinolinolato)aluminum(III) (AlQ3) was then deposited        onto the light-emitting layer. This material was also evaporated        from a tantalum boat.    -   7. On top of the AlQ₃ layer was deposited a 220 nm cathode        formed of a 10:1 volume ratio of Mg and Ag.

The above sequence completed the deposition of the EL device. The devicewas then hermetically packaged in a dry glove box for protection againstambient environment.

Samples 2 and 3 were fabricated in an identical manner to Sample 1except emitter Inv-1 was used at levels indicated in the table. Sample 4was fabricated in an identical manner to Sample 1 except compound Inv-1was not included. The cells thus formed were tested for luminance andcolor at an operating current of 20 mA/cm² and the results are reportedin Table 1 in the form of luminance, emission wavelength and CIE(Commission Internationale de L'Eclairage) coordinates TABLE 1Evaluation Results for EL devices. Inv-1 Luminance Emission Sample (%)(cd/m²) λmax CIEx CIEy Type 1 2 3201 496 0.233 0.602 Invention 2 4 3511496 0.238 0.606 Invention 3 6 3016 496 0.246 0.603 Invention 4 0 113 4560.184 0.210 Comparison

As can be seen from Table 1, all tested EL devices incorporating theinvention emitting material demonstrated a superior green color andhigher luminance relative to the comparative device without thematerial.

DEVICE EXAMPLE 2 Comparative

An EL device, Sample 5, was constructed and evaluated in the same manneras Sample 1 described above, except Com-1 was used in place of Inv-1.Samples 6 and 7 were prepared and evaluated in the same manner as Sample5, except emitter Com-1 was used at the level indicated in Table 2.TABLE 2 Com-1

Evaluation Results for EL devices. Com-1 Lumiance Efficiency SampleLevel (%) (cd/m²) (W/A) CIEx CIEy Type 5 2 424 0.019 0.249 0.457Comparison 6 4 595 0.025 0.296 0.489 Comparison 7 6 711 0.030 0.3300.498 Comparison

As can be seen from. Table 2, all tested EL devices incorporating thecomparative phosphorescent organometallic material demonstrated poorefficiency.

The invention has been described in detail with particular reference tocertain preferred embodiments thereof, but it will be understood thatvariations and modifications can be affected within the scope of theinvention. The entire contents of the patents and other publicationsreferred to in this specification are incorporated herein by reference.

Parts List

-   101 Substrate-   103 Anode-   105 Hole-Injecting Layer (HIL)-   107 Hole-Transporting Layer (HTL)-   109 Light-Emitting Layer (LEL)-   110 Hole-Blocking Layer (HBL)-   111 Electron-Transporting Layer (ETL)-   113 Cathode

1. An electroluminescent device comprising a light-emitting layercontaining a light emitting material that contains an organometalliccomplex comprising a metal selected from the group consisting of Pt, Pdand Ir, and a tridentate (N{circumflex over ( )}C{circumflex over ( )}N)ligand, wherein the tridentate (N° CAN) ligand represents a ligand thatcoordinates to the metal through a nitrogen donor bond, a carbon-metalbond, and a nitrogen donor bond, in that order, wherein at least one ofthe nitrogen donors is part of an aromatic ring or an imine group. 2.The device of claim 1 wherein the metal is Pt.
 3. The device of claim 1wherein the organometallic complex is part of a compound containing twoor more complexes.
 4. The device of claim 1 wherein each of the nitrogendonors is part of an aromatic ring.
 5. The device of claim 1 wherein theorganometallic complex can be represented by Formula (1a),

wherein: Ar^(a), Ar^(b), and Ar^(c) independently represent the atomsnecessary to form a five or six-membered aromatic ring group; and L isan anionic ligand.
 6. The device of claim 5 wherein Ar^(a), Ar^(b), andAr^(c) independently represent the atoms necessary to form asix-membered aromatic ring group.
 7. The device of claim 5 whereinAr^(a) and Ar^(c) independently represent the atoms necessary to form apyridine ring group.
 8. The device of claim 5 wherein Ar^(b) representsthe atoms necessary to form a benzene ring group.
 9. The device of claim5 wherein L represents halogen.
 10. The device of claim 5 wherein Lrepresents a substituent that forms a carbon-platinum bond.
 11. Thedevice of claim 5 wherein L represents an alkynyl group, an alkenylgroup, an aryl group, or an alkyl group.
 12. The device of claim 5wherein L represents RX, wherein X represents a substituent that forms abond to platinum and wherein X represents N, O, S, or Se, and Rrepresents a substituent.
 13. The device of claim 1 wherein theorganometallic complex is represented by Formula (1b),

wherein, Z¹-X¹¹ represent hydrogen or independently selected substituentgroups, provided that adjacent substituent groups can combine to formrings, and provided that Z⁴ and Z⁵, and Z⁷ and Z⁸ can also combine toform rings; and L represents an anionic ligand.
 14. The device of claim13 wherein L represents halogen, an alkynyl group, an alkenyl group, anaryl group, an alkyl group, or RX, wherein X represents a substituentthat forms a bond to platinum and wherein X represents N, O, S, or Se,and R represents an aryl group, an alkyl group, a carbonyl group or asulfonyl group.
 15. The device of claim 1 wherein the organometalliccomplex can be represented by Formula (1c),

wherein, Z¹-Z¹¹ represent independently selected substituent groups,provided that adjacent substituent groups can combine to form rings, andprovided that Z⁴ and Z⁵, and Z⁷ and Z⁸ can also combine to form rings;and R¹-R⁵ represent hydrogen or independently selected substituents,provided that adjacent substituent groups can combine to form rings. 16.The device of claim 15 wherein R¹ and R² of Formula (1c) combine to forma six-membered ring group.
 17. The device of claim 15, wherein R¹ ofFormula (1c) is a 1-12 carbon alkyl group.
 18. The device of claim 13,wherein R¹ and R², of Formula (1c), combine to form a six-membered ringgroup.
 19. The device of claim 13, wherein R³ and R⁴ also combine toform a six-membered ring group.
 20. The device of claim 13, wherein R¹and R³ independently represent a 1-12 carbon alkyl group.
 21. The deviceof claim 1 wherein the light-emitting material is disposed in a hostmaterial.
 22. The device of claim 21 wherein the light emitting materialis present in an amount of up to 50 wt % based on the host.
 23. Thedevice of claim 21 wherein the light emitting material is present in anamount of up to 15 wt % based on the host.
 24. The device of claim 1capable of emitting white light.
 25. The device of claim 24 including afiltering means.
 26. The device of claim 1 including a fluorescent whitelight emitting material.
 27. The device of claim 1 wherein theorganometallic complex contains a quinolinyl or isoquinolinyl group. 28.A display comprising the OLED device of claim
 1. 29. An area lightingdevice comprising the OLED device of claim 1.